Synthesis of new nf compounds

ABSTRACT

A NOVEL PROCESS FOR THE PRODUCTION OF NF COMPOUNDS WHICH COMPRISES REACTING A CONJUGATED DIENE WITH A CONPOUND HAVING THE FORMULA   (I) F2N-R6   WHEREIN R6 IS   -CN, -C(-NF2)=NF OR -C(-F)=NF   RADICAL IS DISCLOSED AS ARE THE NOVEL COMPOUNDS PRODUCED THEREBY.

United States Patent Office 3,594,385

Patented July 20, 1971 Examples of compounds represented by Formula IIand 3,594,385 III include SYNTHESIS OF NEW NF COMPOUNDS Thomas HarlandBrownlee, Westport, Conn., assignor to American Cyanamid Company,Stamford, Conn.

No Drawing. Continuation-impart of abandoned applica- 5 E fion Ser. No.578,420, Sept. 2, 1966. This application CH2 CH2 CH Aug. 2, 1967, Ser.No. 660,870

Int. Cl. 007a 29/26, 31/42, 27/00 I l l I U.S. Cl. 260-290 2 Claims/C\\NF2 /C NFZ /CNF2 CHI NF, CH F on F ABSTRACT OF THE DISCLOSURE Anovel process for the production of NF compounds "f which comprisesreacting a conjugated diene with a com- CH CH CH pound having theformula E IL l-NEE i Z CNF2 i s-NF, wherein R is CE NF H NF, H F

(1) a GEN, (2) a (|3=NF or (3) a (|3=NF JBHn NF2 F CH3 CBHU radical isdisclosed as are the novel compounds produced l 0 thereby. \IIIF l \IFFGHQ CROSS-REFERENCE TO RELATED APPLICATIONS fiq fiq 0H3 This applicationis a continuation-in-part of my copend- I NF? 0E2 NF2 ing application,Ser. No. 578,420, filed Sept. 2, 1966, now CH3 8 l7 abandoned. CH

The starting materials represented by Formula I, above, I 3 as 'well asmethods for their production, are disclosed in 052 Oil CE copending US.application, Ser. No. 280,492, filed May N N N 9, 1963, by Frrthetal. IIL /II l BACKGROUND OF THE INVENTION CH2 CH CH The search for compoundshaving a high nitrogen and (IE3 fluorine content has been, in recentyears, greatly intensified. Compounds of this type have found use ascompo- E 3 a n I n nents in high energy rocket fuels and, for thisreason, have C CH 0 become important. 40

SUMMARY OF THE INVENTION I I L IL I have now discovered a novel group ofcompounds C which have a high nitrogen and fluorine content and are CH HI H therefore useful in the fields specified above. Furthermore, 3 a B17 although they are usually liquids, they may be easily con- CH, CH,verted to solid oxidizers by known methods. CH2 DESCRIPTION OF THEINVENTION INCLUDING CH: 0H3

PREFERRED EMBODIMENTS CH3 E CH3 JFNFZ 02H As mentioned above, the novelcompounds claimed C H CH herein are prepared by reacting a conjugateddiene, such I Z l as butadiene, with a compound represented by Formula02115 0113 I. My novel compounds are represented by the formulae R R CH;CH CH (3H ('3 E \N 081117/ \N \\N l (J-NF (%NF (LNF (II) T \M and (III)T \M 2 2 02115 (4 2 RL R2 (IJH OH H CH (3 CH3 1 1 R3 CH3 wherein 'R, R Rand R are, individually, hydrogen or CH; JH OH an alkyl radical and M isa CH; F 0H, F

mgr N CH3 /(J NFZ 08H" /C\\NF2 CH3 Z/CNF2 or II CH2 F on NF2 H NF,

I -C-NF2 CH3 radical wherein R and R are, Individually, NF or Fradicals. and the like.

The products of Formulae II and III are produced by reacting the dieneand Formula I compound, in the liquid or vapor phase, i.e. the reactantsare mixed together at a temperature such that the resultant mixture is aliquid 4 EXAMPLE 1 Equimolar amounts of perfluoroguanidine andcyclopentadiene are condensed together at 196 C. into a suitable sealedreaction vessel which has been purged with f f -32 aif It Is a g to i initrogen. The resultant liquid mixture is allowed to remain O a Cu q ecompou? 5 en mac m under autogenous pressure at 25 C. for 2 hours. Thefrom about 15 minutes to 7 days depending upon the temresultant producthas the formula perature to which the mixture 15 warmed, 1.e. the lowerthe temperature, the longer the reaction time.

The reaction is conducted in a sealed reaction vessel 10 and in theabsence of oxygen or moisture. Although N subatmospheric or atmosphericpressures are tolerable, it is preferred to conduct the reaction under aslight pres- C-Nl sure.

Examples of suitable compounds represented by Formula I includedifluorocyanamide, perfluoroguanidine and perfiuoroforrnamrdlne. I andhas the following properties; 1 mm. vapor pressure a p of sultgableqoniugated dlenes whlch may be at c., LR. absorptions at: 7.6, 10.2,10.4, 11.1, 11.4, used, include butadiene, isoprene, 1,3-cyclohexane,cyclo- 125, and others 19 pentadiene, alkylated butadienes, i.e.2,3-dirnethylbuta- 20 and +783 (CF13 dlene, 2,3-d109ty1butad1ene and thellke- Analysis.-Calcd for c rl N F (percent): F, 44.2; N, The followingexamples are set forth for purposes of 195 Found (percent); F, N,illustration only and are not to be construed as limitations Following hprocedure f Example 1, Various other 011 the instant invention P andPercentages are y 25 conjugated dienes are reacted with compounds ofFormula weight unless otherwise specified. I. The results are set forthin Table 1, below.

TABLE I Ex. Diene Formula I compound Product Properties I 2...-..Cyclopentadiene Pertiuoroformamldine NF Brown liquid, infrared andfluorine and proton NMR eoni sistant with assigned structure.

N F a 3 2,3-dimethylautadiene.. Difluorocyanamide..... GH -AW Liquid.

4 Isoprene lerfluoroguanldine T-F Do.

i CH C-NF2 5 1,3-butadiene .io Do.

i '\/(|3NF2 6 ..do Pertluoroiorrnamidlne.- lTIF Do.

I Ii-NF:

7...... Cyclopentadiene Difluorocyanamlde N Clear liquid, B.P. -70 CJlmn1. pressure; H'NMRm; 3.21 233 4.17, 5.96, 7.15; W NMR: -44.9 p.p.m.(CF01; int. st CNFB 3 1,3-butadiene .-do

Oily liquid.

VC-N F 2 9 2,3-dimethylbutadiene. Periluoroguanldine NF Clear liquid,HNMR (1); 5.77, 6.07, 7.09, 8.32; F19 NMR:

\ -2e.3, +fi3.4 p.p.m. (CF01; int. std.).

(|.NF2 NF;

The novel compounds of the instant invention can, as mentioned above, beutilized as components in rocket propellant compositions in accordancewith general procedures, well known to those skilled in the art.Conventional oxidizers such as nitric acid, oxygen, ammoniumperchlorate, potassium perchlorate, sodium perchlorate, ammoniumnitrate, etc. may be utilized in conjunction with the novel oxidizersdisclosed herein. One would generally utilize from about 1% to about 35%of my novel compounds in the composition along with an artificial bindersuch as polybutadiene-carboxylic acids, nitrocellulose, polyesters,polyurethanes and the like, in amounts of from about 2040% by weight.Additionally, one can add such fuels as aluminum, beryllium, boron, etc.to the propellant compositions. Further details concerning theproduction and formulation of such rocket propellant compositions can befound in one or more of the following US. patents which are herebyincorporated herein by reference: US. 2,622,277; 2,646,596; 3,132,978.

EXAMPLE 10 To a suitable mixing vessel are added 29.5% of ammoniumperchlorate, 26.3% of powdered aluminum, 34.2% of a commerciallyavailable polyester binder resin (mixed with sufiicient cross-linkingagent) and 10.0% of the compound of Example 1. After heating at 70 C.for 96 hours to cross-link the resin, a tough, propellant composition isrecovered.

EXAMPLES 11-18 Following the procedure of Example 10, the products ofExamples 2-9 were incorporated into rocket propellant compositions inplace of the Example 1 product used therein. In each instance, tough,stable products were obtained.

I claim:

1. A compound represented by a formula selected from the groupconsisting of (1) and (2) wherein R, R R and R are, individually,selected from the group consisting of hydrogen and an alkyl radical andM is selected from the group consisting of radicals, R and R beingselected from the group consisting of NF and F.

2. A method for the production of a compound of claim 1 which comprisesreacting a conjugated diene with a compound having the formulaReferences Cited UNITED STATES PATENTS 3,215,709 11/1965 Logothetis260349 OTHER REFERENCES Mitsch: I. Am. Chem. Soc., vol. 87, pp. 328 to333 (1965).

LELAND A. SEBASTIAN, Primary Examiner US. Cl. X.R.

